Ethers for use in lubricants and hydraulic fluids



United States Patent Ofiice 3,344,195 Patented Sept. 26, 1967 3,344,195 ETHERS FOR USE IN LUBRICANTS AND HYDRAULIC FLUIDS Lloyd I. Osipow, New York, Frederick J. Brashear, Brooklyn, and William Rosenblatt, Spring Valley, l l.Y., assignors to Fats and Protein Research Foundation, Inc., Chicago, 1H,, a corporation of Illinois No Drawing. Filed May 13, 1963, Ser. No. 280,095 6 Claims. (Cl. 26tl611) The invention relates to novel isomeric mixtures of a product having a formula selected from the group consisting of R II wherein R is selected from the group consisting of alkoxy radicals having 1 to 18 carbon atoms, phenyl and alkylphenyl radicals having 1 to 8 alkyl carbon atoms, R, is selected from the group consisting of hydrogen, alkoxy radicals having 1 to 8 carbon atoms, phenyl and alkylphenyl radicals having 1 to 8 alkyl carbon atoms, x is an integer from 6 to 8 and y is an integer from 8 to 10. The invention also relates to novel high temperature organic lubricants and hydraulic fluids having the said isomeric mixtures as a 'base stock.

To meet the requirements of todays high speed aircraft, a great amount of time, money and effort have been expended to develop high temperature lubricants and hydraulic fluids. Conventional synthetic diester lubricants derived from octyl and nonyl alcohols and adipic, azelaic and sebacic acids are satisfactory up to temperatures of about 300 F. while triester lubricants based on trimethylol propane are satisfactory up to temperatures of about 400 C. Also substances, such as silicones, fluorocarbons, polyphenyl ethers and super-refined mineral oils have been proposed as possible base stocks for high temperature lubricants and hydraulic fluids but they suffer from various defects.

It is an object of the invention to provide novel isomeric mixtures of products of Formulas I, II and III.

It is another object of the invention to provide novel processes for the preparation of products of Formulas I, II and III.

R III wherein R is selected from the group consisting of alkoxy radicals having 1 to 18 carbon atoms, phenyl and alkylphenyl radicals having 1 to 8 alkyl carbon atoms, R is selected from the group consisting of hydrogen, alkoxy radicals having 1 to 8 carbon atoms, phenyl and alkylphenyl radicals having 1 to 8 alkyl carbon atoms, x is an integer from 6 to 8 and y is an integer from 8 to 10. Particularly preferred are the products when x is 7 and y is 9 since they can be prepared from oleyl alcohol whose cost is low due to its abundance in nature.

The novel products of the invention are derived from mono-unsaturated alcohols, such as oleyl'alcohol by adding substituents across the double bond. Using oleyl alcohol as an example, the substituents add mainly at the ninth and tenth carbon atoms but since the double bond is labile, some shifting of the double bond occurs and addition occurs in other places in the molecule. Therefore, the products of the invention are mixtures of many 1S0- mers.

The novel products show negligible thermal decomposition at temperatures up to 700 F., have low pour points and a good viscosity index and are excellent base stocks to which various known additives may be added for detengency, lubricity, pour point depression, corrosion inhibition, oxidation inhibition, etc. to form high temperature lubricants and hydraulic fluids.

The novel products of the invention can be prepared in a variety of Ways starting from the corresponding unsaturated alcohol. Using oleyl alcohol as an example, it may be reacted with hydrogen bromide to form oleyl bromide which can then be used to prepare isomeric mixtures of compounds of Formula I and II. Oleyl bromide may be reacted with benzene or alkylated benzene in the presence of aluminum chloride to form 1,10-diphenyl or substituted phenyl-octadecane or it may be reacted with an alkali metal lower alkoxide to form l-lower alkoxy-9 octadecene which can be hydrobrominated and reacted with an alkali metal lower alkoxide to form 1,10-dilower alkoxy-octadecane. Oleyl bromide can also be reacted with magnesium to form oleyl magnesium bromide and the latter hydrolyzed to form 9-octadecene which can be hydrobrominated and then reacted with an alkali metal lower alkoxide to form lO-lower alkoxy-octadecane. Oleyl bromide can also be reacted with sodium to form 9,27-hexatriacontadiene which upon hydrobromination and reaction with an alkali metal lower alkoxide forms 9,28-dilower alkoxy-hexatriacontane.

Oleyl alcohol can also be reacted with benzene or alkylated benzene in the presence of aluminum chloride to form IO-phenyl or alkylated phenyl-octadecanol which can be reacted with hydrogen bromide to form the corresponding lO-aryl-octadecyl bromide. The latter can be reacted with magnesium and then be hydrolyzed to form the corresponding 10-aryl octadecane or it can be reacted with sodium to form the corresponding 9,28-diarylhexatriacontane.

The ether compounds of Formula III may be prepared by reacting oleyl alcohol with boron trifluoride to form dioleyl ether which can be reacted with benzene or alkylated benzene in the presence of aluminum trichloride to form the corresponding l0,l0'-diaryl-di-octadecyl ether or which can be hydrobrominated and reacted with an alkali metal lower alkanolate to form lO,10'-dilower alkoxy-di-octadecyl ether.

In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.

Commercial grade oleyl alcohol (Novol) ,having an iodine value of 91.1 and having a refractive index 3 n L4571 was reacted with benzene and aluminum chloride under Friedel-Crafts reaction conditions to form 10-phenyl-octadecanol having a boiling point of 198-204 C. at 1 mm. Hg and a refractive n 1.4910.

Anhydrous hydrogen bromide was slowly added to the 10-phenyl-octadecanol at 100 to 110 C. for four hours. The reaction mixture was then washed successively with cold sulfuric acid, 50% methyl alcohol, 15% ammonia and 50% methyl alcohol to obtain 10-phenyloctadecyl bromide as a clear yellow liquid having a boiling point of 185 to 190 C. at 0.2 mm. Hg and a refractive index n ='l .495 0.

Analysis.Calculated for C H Br: Percent Br (calculated), 19.5. Found, 19.3.

Step B: Preparation of l-phenyl-octadecane.110 gm. (0.27 mol) of the 10-phenyloctadecyl bromide produced in Step A were added dropwise over a period of thirty minutes to 0.3 mol of magnesium turnings in 500 cc. of anhydrous ether. The mixture was warmed slightly to initiate the reaction and after all the said bromide had been added, the reaction mixture was refluxed for four hours. The reaction mixture was cooled in an ice bath and the reaction mixture was hydrolyzed by the careful addition of first 100 cc. of a cooled 14% ammonium chloride solution and then 100 cc. of 5% hydrochloric acid. The ether solution wasthen washed until neutral and dried over sodium sulfate.

Upon distillation of the ether solution at 0.5 mm. Hg, 44 gm. of a colorless liquid fraction at 166 to 172 C. was obtained which was an isomeric mixture of phenyl-octadecane having a refractive index of The yield was 49% based on the 10phenyl-octadecyl bromide.

Analysis.C H Calculated: C, 87.2; H, 12.8. Found: C, 87.0; H, 13.2.

EXAMPLE II Preparation of isomeric mixtures of 10-(tert.-bzttylphenyl -0ctadecane Step A: Preparation of 10-(terl.-butylphenyl) -octadecyl bromide.-Commercial grade oleyl alcohol (Novol) was reacted with tert.-butyl benzene having a boiling point of 167.5 to 170.5 C. and aluminum chloride under Friedel-Crafts reaction conditions to form 10-(tert.-butylphenyl)-octadecanol as an amber fluorescent oil having a boiling point of 211 to 215 C. at 0.8 mm. Hg and a refractive index n =*1.4975.

Anhydrous hydrogen bromide was slowly added to the 10-(tertsbutylphenyl)-octadecanol at 100 to 110 C. for four hours and the reaction mixture was then washed successively with cold sulfuric acid, 50% methyl alcohol, ammonia and 50% methyl alcohol to obtain 10 (tert.-butylphenyl)-octadecyl bromide having a boiling point of 215 to 220 C. at 0.2 mm. Hg.

Analysis.C H Br, percent Br, Calculated: Found: 17.3.

Step B: Preparation of 10-(tert.-butylphenyl)-0ctadecane.0.27 mol of 10-(tert.-butylphenyl)-octadecyl bromide produced in Step A was added to 0.3 mols of magnesiurn turnings in 500 cc. of anhydrous ether over a period of thirty minutes while slightly warming the reaction mixture. After all of the said bromide had been added, the reaction mixture was refluxed for four hours. The reaction mixture was cooled in an ice bath and the reaction mixture was hydrolyzed by the careful addition of a cooled 14% ammonium chloride solution and then 5% hydrochloric acid. The ether solution was washed until neutral and dried over sodium sulfate.

Upon distillation of the ether solution at 0.5 mm. Hg, 10-(tert.-butylphenyl)-octadecane was obtained in 35% yield as a light yellow oil having a refractive index of n =1.4900.

EXAMPLE III Preparation of isomeric mixture of 9,28-dimeth0xyhexatriacontane S tep A: Preparation of 9,28-a'ibr0m0-hexatriac0ntane.-- Oleyl alcohol was reacted with phosphorus tribromide in carbon tetrachloride at 10 to 0 C. according to the method of Deathenage et al. (J.A.C.S., vol. 61, 1939, p. 630). After the removal of the carbon tetrachloride, the residue was distilled through a 30 cm. Vigreaux colmun and oleyl bromide having a trace odor of phosphine was obtained as the fraction boiling at to C. at 0.5 mm. Hg.

Anolysis.C H Br, percent Br, Calculated, 24.1. Found, 23.5.

A fine suspension of sodium was obtained by refluxing a mixture of 17.5 gm. (0.76 mol) of sodium and 200 cc. of dry toluene. 165 gm. (0.5 mol) of the oleyl bromide were added in small increments over a period of one hour to the suspension and then the reaction mixture was refluxed for 24 hours. The excess sodium was decomposed with cold dilute hydrochloric acid and the toluene layer was washed with saturated solutions of sodium chloride, sodium bicarbonate and water. The toluene layer was dried over sodium sulfate and the solvent was removed by distillation. The crude residue of 111.5 gm. was recrystallized from acetone at 25 C. to yield 26.1 gm. of 9,27-hexatriacontadiene having a wax-like consistency melting at 44 to 45 C. and 58.0 gm. of an acetone insoluble oil. Fractionation of the said oil did not yield any 9,27-hexatriacontadiene.

9,27-hexatriacontadiene was hydrobrominated by the free radical hydrobrornination method of Jungermann et al. (J. Am. Oil Chemists Soc., vol. 35, 1958, p. 393). 9,27-hexatriacontadiene in benzene was reacted with hydrogen bromide in the presence of benzoyl peroxide as the catalyst at room temperature to obtain an isomeric mixture of 9,28-dibromohexatriacontane as a dark amber oil.

Analysis.-C H Br percent Br, Calculated, 24.1. Found, 22.9.

Step B: Preparation of isomeric mixtures of 9,28-dimethoxyhexatriacontone-40.0 gm. (0.06 mol) of the isomeric mixture of dibromohexatriacontane and 6.5 gm. of sodium methoxide in 15 cc. of anhydrous methanol were added to a 300 ml. round bottom flask equipped with a mechanical stirrer and a reflux condenser fitted with a calcium chloride drying tube. After the initial reaction had subsided, the reaction mixture was refluxed on a water bath for four hours. The reaction mixture was cooled and 20 ml. of ice water were added. The crude product was extracted with ether and the ether extract was washed with water until a test for bromide ion was negative. After drying the ether extract over calcium chloride, the ether was removed to obtain 26.0 gm. (77% yield) of an isomeric mixture of 9,28-dimethoxy-hexatriacontane having a refractive index 11 =1.4654.

Analysis.C H- O Calculated: C, 80.5; H, 13.9. Found: C, 79.6; H, 13.5.

EXAMPLE IV Preparation of isomeric mixture of 9,28-di-(2-ethylhexoxy -hexalriac0ntane Using the process described in Example III, 9,28-dibromo-hexatriacontane was reacted with the sodium derivative of 2-ethylhexyl alcohol to form an isomeric mixture of 9,28-di-(Z-ethylhexoxy)-hexatriacontane which after recrystallization from ethanol and then acetone had a melting point of 18 C.

Anaylsis.C H O Calculated: C, H, 14.0. Found: C, 82.6; H, 13.3.

' metlzoxy dioctadecyl ether.l02.0

EXAMPLE V Preparation of isomeric mixtures of LZO-diphenyloetadecane 191.9 gm. (0.58 mol) of oleyl bromide prepared as in Step A of Example III were dissolved in 250 cc. of anhydrous benzene and the resulting solution was added slowly over a period of four hours to a stirred solution of 170 gm. (1.28 mols) of anhydrous aluminum chloride in 750 cc. of benzene at 35 C. The mixture was then stirred at 65 to 70 C. for two hours and was then cooled and hydrolyzed with cold dilute hydrochloric acid. After removing the benzene by steam distillation, 66 gm. (28% yield) of an isomeric mixture of 1,10-diphenyl-octadecane were obtained as a red oil distilling at 178 to 180 C. at 0.2 mm. Hg and having a refractive index Analysis.C H4s, Calculated: C, 88.6; H, 11.4. Found: C, 88.9; H, 11.0.

EXAMPLE VI Preparation of isomeric mixture of 1,10-di-(tert.-butylphenyl)-octad ecane Found: C, 87.9; H, 12.2.

EXAMPLE VII Preparation of isomeric mixture of 10,10- dimethoxy-dioctadecyl ether Step A: Preparation of dioleyl ether.537 gm. (2.0 mol) of oleyl alcohol and 72 gm. (0.51 mol) of boron trifluoride ethyl ether were placed in a 2-liter round bottom flask equipped with a reflux condenser, a mechanical stirrer and a calcium chloride drying tube. The solution was refluxed for four hours at 180 C. and then cooled to room temperature. The crude product was extracted with ethyl ether and the ether extract was washed with water until neutral and then was dried over sodium sulfate. After removing the solvent by distillation, dioleyl ether was collected as a viscous oil boiling at 278- 290 C. at 1 mm. Hg. Upon recrystallization of the prod not from acetone, 122.5 gm. (47% yield) of dioleyl ether were obtained as a white solid having a melting point of 34 to 35 C., a refractive index n =1.4550 and a hydroxyl value of 3.9.

Step B: Preparation of isomeric mixture of 10,10'-dibromodioctadecyl ether.Dioleyl ether was reacted with hydrogen bromide in benzene at room temperature in the presence of a benzoyl peroxide catalyst for six .hours to form 10,10'-dibromo dioctadecyl ether. The reaction was exothermic. The product was washed with water until neutral and then was dried over calcium chloride.

Analysis.-C H OB1 percent Br, Calculated, 23.5. Found, 22.0.

Step C: Preparation of isomeric mixture of 10,10'-digm. (0.15 mol) of l0,10-dibromo di-n-octadecyl ether and 16.2 gm. (0.3 mol) of sodium methoxide were added with stirring to a three-neck flask eqiupped with a mechanical stirrer and a reflux condenser fitted with a drying tube. After the initial reaction had subsided, 20 cc. of dry methanol were added to the flask and the mixture was refluxed on a water bath for 9 hours. The reaction mixture was cooled and cold water was cautiously added. The product was washed successively with water, sodium bicarbonate solution and water and was then dried over sodium sulfate. After removing the ether by evaporation, an amber oil was obtained which was treated with decolorizing charcoal and .purified by absorption on an alumina column 6 t t f'rcm a hexane solution. 34.9 gm. (40% yield) of 10,10- dimethoxy-di-n-octadecyl ether were obtained as a light amber oil having a refractive index of n =1.4634.

Analysis.C H O Calculated: C, 78.3; H, 13.5. Found: C, 78.2; H, 13.1.

EXAMPLE 1X Preparation of isomeric mixture of 10,10'-di-(tert.- butoxy)-di-n-octadecyl ether Using the procedure of Example VII, 10,10-dibromodi-n-octadecyl ether was reacted with sodium tert.-butoxide to obtain a 26% yield of 10,10"-di-(tert.-butoxy)- di-n-octadecyl ether having a refractive index Analysis.C .,H O Calculated: C, 79.2; H, 13.6. Found: C, 79.0; H, 13.3.

EXAMPLE X Preparation of isomeric mixtures of 10,10'-di-(2-ethylhex0xy)-di-n-octadecyl ether Using the procedure of Example VII, 10,10'-dibromodi-n-octadec'yl ether was reacted with sodium Z-ethylhexoxide to obtain a 39% yield of 10,10'-di-(2'-ethylhexoxy)-di-n-octadecyl ether having a refractive index n =1.4635.

Analysis.C H O Calculated: C, 80.1; H, 13.7. Found: C, 79.8; H, 13.3.

EXAMPLE XI Preparation of isomeric mixtures of 10,10'-di-(tert.-

butylphenyl)-di-n-oetadecyl ether 145 gm. (0.28 mol) of oleyl ether prepared as in Example VII, Step A, dissolved in 250' cc. of tert.-butyl benzene were added to a stirred solution of 82.6 gm. (0.62 mol) of anhydrous aluminum chloride in 250 cc. of tert.- butyl benzene at a temperature not greater than 35 C. The mixture was then heated to 80 C. and stirred for 10 hours and then was cooled and hydrolyzed with dilute hydrochloric acid. The excess tert.-butyl benzene was removed by steam distillation and the product was taken up in ethyl ether which was then dried over sodium sulfate. 10,10-di-(tert.-butylphenyl)-di-n-octadecyl ether was obtained as a red oil distilling at 215 to 233 C. at 0.5 mm. Hg.

Analysis.C H O, Calculated: C, 86.3; H, 11.6. Found: C, 86.1; H, 11.4.

EXAMPLE XII Preparation of isomeric mixtures of 9,28-diphenylhexatriacontane 81.8 gm. (0.2 mol) of 9-phenyl-octadecyl bromide as prepared in Example I are added to a stirred suspen sion of 1.15 gm. (0.05 mol) of clean sodium in dry toluene at reflux temperature and the reaction mixture was refluxed for 24 hours during which a characteristic blue color developed. After cooling the reaction mix ture, cold dilute hydrochloric acid was added to decompose the excess sodium and the solution was then washed with water until neutral and was dried over calcium chloride. After removing the toluene by vacuum distillation, the product was dissolved in hexane and passed several time through a chromatographic column of alumina. 23.0 gm. (35% yield) of 9,28-diphenylhexatriacontane were obtained as a clear yellow oil having a refractive index n =1.487l and an iodine octadecyl bromide prepared as in Example II was reacted with sodium to obtain a 26% yield of 9,28-di-(tert.-

7 butylphenyl)-hexatriacontane having a refractive index 71 1.4910.

EXAMPLE XIV Preparation of isomeric mixtures of IO-ethoxyling at 153 to 168 C. at 0.2 mm. Hg having a refractive index n =1.4S90.

Analysis.-C H O, Calculated: C, 83.5; H, 12.5. Found: C, 82.9; H, 12.9.

octadecane 5 EXAMPLE XVII Oleyl magnesium bromide prepared from oleyl bro- Preparation of isomeric mixture of J-methoxymide was hydrolyzed to obtain 9-octadecene having a ZO-(terL-butoxy)-ctadecane bolhng point of 125 to 1 at H Oleyl bromide was reacted with sodium methoxide to decene was then reacted fi hydrogen brormde m t e 10 obtain a 69% yield of 1-methoxy-9-octadecene having a presence ofabenzoyl perox de catalyst to form lO-bdromoboiling point of 136 to 140C at mm Hg and oct'fldecane' Sodmm ethoxlde and lo'bromgiocta .3 i a refractive index n =l.45l0. The latter product was Wale reacted to lo'ethoxy'optadecane' The P reacted with hydrogen bromide in the presence of a products were Punfied by pagsmg hexane 5 benzoyl peroxide catalyst to obtain a 57% yield of 1- through Several chromatographlc Columns of alumna methoxy-lO-bromo-octadecane having a boiling point of After removal of the solvent, IO-ethoxy-octadecane was 178 to C at 02 Hg and a refractive index gi zf clear Yellow 011 havmg a refractive Index n =l.47l5. The latter was recated with tert.-butanol and sodium to obtain a 30% yield of l-methoxy-lO- Anaiys1s.C I-I O, Calculated: C, 80.2; H, (tert.-butoxy)-octadecane having a boiling point of 164 Found to 170 C. at 0.2 mm. Hg and a refractive index EXAMPLE XV nD =1.46S0. Preparation of isomeric mixtures of 1,10-di- Anaysls' C2:fH48O2 calculated: 779;

Found. C, 77.2, H, 12.9. tert.-but0xy -0ctadecane Oleyl bromide was reacted with sodium tert.-butoxide Lubrwmmg fi dam to form 1-tert.-butoxyoctadecene which was then re- T VISCOSIW lndeX, P Polnts and the thermal acted with hydrogen bromide in the presence of a benzoyl bllltX 0f the wmpounds of Examples t0 XVH were peroxide catalyst to f 1-te t -b t 10-b t termined as follows. The viscosity indices were determined decane. The latter was then reacted with sodium tert.- according to ASTM 13567-53 and the P Points were butoxide to obtain l,l0-di-(tert.-butoxy)-octadecane as 'detefmmed y ASTM 1397-57. a colorless oil distilling at 170 to 182 c. at 0.2 mm. The thermal stability test was effected y Placing a H weighed sample and sample tube into the inner chamber Analysis.C H O Calculated: C, 78.3; H, 13.7. of an Abderhalden drying apparatus. The air in the sys- Found: C, 78.0; H, 13.5. tem was evacuated and nitrogen was admitted thereto. A EXAMPLE XVI small positive pressure of nitrogen was maintained on the system during the entire test. The Arochlor 1254 in the l isomer 1C f apparatus was brought to reflux at about 690 F. and was bufoxy'lo'phenyl'ocmdecane maintained there for ten hours after which the samples loh yl etad yl b id as produced i Example and contents of the inner chamber were collected, re- I was reacted with sodium tert.-but0xide to obtain a weighed and the percent loss calculated. The test results 65% yield of l-tert.-butoxy-l0-phenyl-octadecane distilare summarized in Table I.

TABLE I Oetadecanes Wherein- Viscosity, cs: After 10 hours at 690 F.

Isomerie Pour Point, ASTM Mixture F. Viscosity Change In Weight R R of Example F. 210 F. Index 100 F. Loss,

Viscosity, Percent Percent Q H 1 +15 11.0 2. 7 s4 13. 6 5. s

C(CH3)3 H 11 +14 25.4 10.5 187 6.3 11.7

Q Q V -25 32. a 4. 1 -s3 8.7 6.2 @Wfifih @(Xomh VI -35 33.0 4.2 -50 2.7 1.0 002115 11 XIV 12 4.4 2.7 310 7.0 o C (01195 0 0 (011m XV 25 5. 5 1. 9 142 -3. 0 14. 4

Q 0 0 01103 XVI -15 5. 5 1. 9 142 -1. s 3. 4 0 0 (CH 0 CH5 XVII +45 11. 3 2. 5 29 0 2. 4

TABLE I.-Continued Viscosity, cs. After hours at 690 F. Isomen'e ASTM Hexatriacontanes wherein R- Mixture of Pour Point, Viscosity Example F. Index Change 111 Weight Loss,

100 F. 210 F. 100 F. Vis- Percent cosity, Percent OCH; III +32 14. 6 4. 3 214 OCgHn IV +45 16. 7 3. 3 50 16. 8 7. 0 Q XII +32 22.4 5.6

Q0 0H3 XIII 0 17.7 a. 7 109 37.8 14. 4

Dioctadecyl Ethers Wherein R- OOHa VII +32 17.0 5. 1 205 14. 4 007115 VIII +45 22. 9 5.0 158 17. 9 4. 2 OC(OH )3 IX +50 19. 6 4. 6 167 2. 0 2.2 OO Hn X +60 22. 7 5. 3 169 45. 0 3. 0 Q0 (CHa)a XI 40. o 4. 7 -2s 4. 2 0.6

*2-ethy1hexyl ether.

The compounds of Formula I are generally preferred since they have lower pour-points. As can be seen from the table, the best compounds tested were 1,10-di-(tert.- butoxy)-octadecane of Example XV and 1-tert.-butoxylO-phenyl-octadecane of Example XVI when considering pour point, viscosity index and thermal stability.

Various modifications of the process and compositions of the invention may be made without departing from the spirit or scope thereof, and it is to be understood that the invention is to be limited only as defined in the appended claims.

What is claimed is:

1. An isomeric mixture of a product of the formula wherein R is selected from the group consisting of phenyl and alkylated phenyl having 1 to 8 alkyl carbon atoms, x is an integer from 7 to 8 and y is an integer of 8 to 9 with the sum of x+y being 16, said product being produced by reacting dioleyl ether with a member selected from the group consisting of benzene and alkylated benzene having 1 to 8 alkyl carbon atoms in the presence of aluminum trichloride.

2. An isomeric mixture of a product of the formula wherein R is alkoxy of 1 to 8 carbon atoms, x is an integer from 7 to 8 and y is an integer of 8 to 9 with the sum of x-l-y being 16, said product being produced by hydrobrominating dioleyl ether in the presence of a benzoyl peroxide catalyst to saturate the double bonds and reacting the resulting product with an alkali metal alkanolate of 1 to 8 carbon atoms.

3. The product of claim 2 wherein R is methoxy.

4. The product of claim 2 wherein R is tert.-butoxy.

5. The product of claim 2 wherein R is 2-ethylhexoxy.

6. The product of claim 1 wherein R is tert.-butylphenyl.

Cosby et al.: Proc. Amer. Petrol. Inst. 22 (III), pp. 12- 16,18 (1941).

Schiessler et al.: Proc. Amer. Petrol. Inst. 26, III, pp. 254, 260, 262, 264, 266 (1946).

LEON ZITVER, Primary Examiner. H. MARS, Asisistant Examiner. 

1. AN ISOMERIC MIXTURE OF A PRODUCT OF THE FORMULA (H3C-(CH2)X-CH(-R)-(CH2)Y)2-O WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF PHENYL AND ALKYLATED PHENYL HAVING 1 TO 8 ALKYL CARBON ATOMS, X IS AN INTEGER FROM 7 TO 8 AND Y IS AN INTERGER OF 8 TO 9 WITH THE SUM OF X+Y BEING 16, SAID PRODUCT BEING PRODUCED BY REACTING DIOLEYL ETHER WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF BENZENE AND ALKYLATED BENZENE HAVING 1 TO 8 ALKYL CARBON ATOMS IN THE PRESENCE OF ALUMINUM TRICHLORIDE. 